FIELD OF INVENTION
[0001] The present invention relates broadly to a system and method for processing an input
fuel gas and steam to produce carbon dioxide and an output fuel gas in separate gas
streams.
BACKGROUND
[0002] Industrial plants that consume large amounts of carbon fuels, such as power, cement
and iron and steel plants, increasingly require flexibility in their operations associated
with the volatility of the cost of fuels and the price of products, as well as the
regulatory and market environment particularly associated with carbon emissions. In
such cases there are benefits to be obtained from adopting a mix of fuels, such as
fossil fuels of coal and natural gas, which attract emissions penalties, and biomass
and waste which typically do not. There is a need for production processes that can
interchange such fuels. Such a flexible fuel plant can operate in any of the regimes
of (a) full carbon emissions from combustion of fossil fuels with no sequestration,
with emissions penalties, (b) with negligible emissions from either combustion of
fossil fuels with sequestration of carbon dioxide (CO
2) or combustion of non-fossil fuels without sequestration, with no emissions penalties
(c) negative carbon emissions from combustion of non-fossil fuels with sequestration
of CO
2, which may be a source of revenue with emissions trading schemes. The optimal operating
conditions may change on the timescale of hours to days due to market variability
in input and output prices, including those from carbon emissions. In addition, there
may be an additional uncertainty in long term operating costs over the timescale of
the lifetime of the industrial plant, potentially rendering the plant uneconomic,
arising from changes to the regulatory environment for CO
2 emissions. In this environment, there is a need for a flexible approach to carbon
capture in which the plant can operate in any of these regimes.
[0003] With the high capital cost of industrial processing plants, the need for flexibility
in the use of the plant is particularly important. For example, an operator may have
a choice of using fuel inputs, such as coals of various grades, natural gas (NG),
biomass or waste. The operator may also benefit from a choice of derived fuel products,
including Hydrogen, Synthetic Natural Gas (SNG), and a choice of whether or not to
process the carbon dioxide for sequestration. There is a need for a flexible process
that can use a variety of fuel inputs to produce a variety of fuel outputs with and
without carbon capture. More specific examples are considered below.
[0004] One approach to reduce CO
2 emissions from the combustion of solid fuels such as coal, biomass and waste is pre-combustion
carbon capture from Syngas produced by the partial oxidation of such solid fuels with
steam and oxygen in a Partial Oxidising Gasifier. Syngas comprises the combustible
gases, hydrogen, carbon monoxide and smaller amounts of methane and other hydrocarbons.
It also contains significant amounts of CO
2 and steam. In this approach, further CO
2 isgenerated by the Water-gas Shift reaction with steam, separated, compressed and
sequestered, with the production of hydrogen as the fuel gas stream. This process
is the basis of the Integrated Gasification Combined Cycle (IGCC) system for power
generation. It is believed that this process, without
CO2 capture, has about the maximum efficiency for power generation. While the Partial
Oxidising Gasifier technology is versatile with respect to the solid fuel source,
decarbonation using pre-combustion capture technologies, such as the Benfield separation
process and the Water Gas Shift reaction, incurs a significant energy penalty, and
the costs of
CO2 capture are significant. In addition, hydrogen is difficult to transport and store,
so that such a system must produce hydrogen on demand. Underground Coal Gasification
produces Syngas directly from a coal seam.
[0005] In both cases, the gasification reaction occurs at high pressure, generally in excess
of 20 bar, and the output temperature is controlled by quenching with water, but is
optimally about 800-900 C, say 850C before gas clean-up. In most commercial Partial
Oxidising Gasifiers, pure oxygen is injected into the Gasifier. The compressed oxygen
is extracted from the air in an Air Separation Unit. In other Partial Oxidising Gasifiers,
compressed air is introduced directly into the gasifier, with the consequence that
the Syngas also contains inert gases such as nitrogen and argon.
[0006] There is a need for a decarbonation technology that can decarbonise Syngas produced
from any of these processes, to produce a decarbonised hydrogen fuel stream, with
or without inert gases, and a separate carbon dioxide gas stream, with a low energy
penalty.
[0007] Another gasifier approach is to hydrogasify the solid fuel with hydrogen, and often
with steam, in a Hydrogasifier to produce a fuel gas which comprises combustible components
methane, carbon monoxide and hydrogen, and smaller amounts of other hydrocarbons.
This fuel gas stream, called herein Hydrogas, can be partially decarbonised to produce
a hydrogen gas stream that is fed back into the Hydrogasifier, a methane rich gas
stream, called Synthetic or Substitute Natural Gas (SNG), and a separate CO
2 stream for sequestration. SNG production is only a partial decarbonisation process,
typically with about 50% decarbonisation, because the SNG carries about 50% of the
initial carbon and the CO
2 the other amount. The decarbonation of Hydrogas removes carbon from CO and CO
2 in the Hydrogas, but not from methane, to ensure that the SNG meets the high Calorific
Value specifications of NG. This partial decarbonation of Hydrogas can be achieved
using established pre-combustion capture technologies, such as the Benfield or amine
processes in conjunction with steam and the Water-Gas Shift reaction. However, this
process incurs a significant energy penalty, so that the costs of
CO2 capture are significant. There is a need for a decarbonation technology that can
partially decarbonise Hydrogas to produce a hydrogen stream, an SNG fuel stream, and
a separate carbon dioxide gas stream, with a low energy penalty. Underground Coal
Hydrogasification produces Hydrogas directly from a coal seam through the injection
of hydrogen, with steam if required. This Hydrogas can be decarbonised as described
above.
[0008] The reduction of emissions from the combustion of NG, and thus SNG, is required to
further reduce the CO
2 emissions. Generally, the carbon emissions from combustion of NG/SNG is about 50%
less of the CO
2 emitted from the combustion of a solid fuel per unit of thermal energy produced.
Further reduction of CO
2 emissions from combustion of NG/SNG can be achieved by post-combustion carbon capture,
for example using amine technology. Pre-combustion decarbonisation of NG/SNG can be
achieved by steam reforming the NG/SNG to produce Syngas, and the Syngas fuel stream
is then decarbonised as described above for Syngas from a Partial Oxidising Gasifier.
This gives a hydrogen gas stream for combustion and a separate carbon dioxide stream
for sequestration. The separate processing steps of Steam Reforming, Water-Gas Shifting
and CO
2 capturing using, for example, the Benfield process, has a significant energy penalty.
There is a need for a decarbonation technology that can decarbonise NG/SNG in a single
reactor to produce a decarbonised hydrogen fuel stream and a separate carbon dioxide
gas stream, with a low energy penalty.
[0009] For example, a power generator may have access to solid fuel from a nearby coal,
biomass or waste resources to produce Syngas from a Partial Oxidising Gasifier, and
also have access to NG from a gas pipeline or from coal seam extraction. In this case,
it may be desirable to have the flexibility to decarbonise either the Syngas or the
NG to give a continuous hydrogen gas stream for power generation.
[0010] In another example, the power generator has chosen to produce SNG from Hydrogas and
may benefit from diverting excess production of SNG into the NG pipeline, if only
to access the gas storage capabilities of typical gas distribution systems. This would
allow the operation of the Hydrogasifier at its maximum capacity even if the demand
for power is low. In this approach, it would be preferable for a single stage process
in which the decarbonation process can be switched from production of hydrogen to
production of SNG, or a separable mixture thereof. Such a system would desirably be
controlled to meet the variable demand for power taking into account the market for
SNG and CO
2.
[0011] US 2006/207177 A1 discloses a process and a system for producing a gas product from a carbonaceous
fuel in a gasifier, the gas product is a CO-rich syngas and undergoes a reaction with
gaseous H
2O to produce H
2 and CO
2 in a water-gas shift reactor, wherein also the CO
2 is captured with CaO in a exothermic reaction to form hot CaCO
3, the hot CaCO
3 is then calcined to produce CO
2 and CaO using the heat content of the hot CaCO
3 in a calciner. A need therefore exists to provide a system and method for processing
an input fuel gas of variable composition, such as Syngas, Hydrogas, NG, SNG or mixtures
thereof with steam to produce an output fuel gas with a controlled composition and
a separate CO
2 gas stream that seek to address at least one of the above mentioned problems.
SUMMARY
[0012] According to a first aspect of the present invention there is provided a system for
processing an input fuel gas and steam to produce separate CO
2 and output fuel gas streams, the system comprising a decarboniser segment configured
such that at least a solid sorbent reacts therein with the fuel gas and steam to remove
carbon from the input fuel gas and to produce the output fuel gas stream in an exhaust
gas from the decarboniser; acalciner segment configured such that the solid sorbent
from the decarboniser segment reacts therein to release the carbon as CO
2 into the CO
2 gas stream; wherein the system is configured such that CO
2 partial pressures and temperatures in the decarboniser and calciner segments respectively
are controlled such that the temperature in the decarboniser segment is higher than
the temperature in the calciner segment such that heat is provided from the decarboniser
to the calciner.
[0013] The decarboniser may be configured such that the steam reacts with carbon monoxide
in the fuel gas, or produced from the fuel gas in the decarboniser, to produce CO
2 for adsorption by the solid sorbent.
[0014] The decarboniser may be configured such that the steam reacts with hydrocarbons in
the fuel gas to produce either or both of the carbon monoxide and the CO
2.
[0015] The system may further comprise a heat exchanger unit for exchanging heat between
the decarboniser and calciner segments; wherein heat provided from the decarboniser
to the calcineris provided through the heat exchanging unit
[0016] The output fuel gas stream may comprise hydrogen or methane.
[0017] The input fuel gas may comprise Syngas, Hydrogas, SNG, or NG.
[0018] A solid catalyst may be provided in the decarboniser segment to activate a reaction
to produce the output fuel gas in the exhaust gas from the decarboniser.
[0019] The solid catalyst may be supported in the decarboniser segment, or mixed with the
solid sorbent as separate particles, or incorporated into the solid sorbent.
[0020] The solid catalyst may comprise iron oxide.
[0021] The solid catalyst may be mixed with the solid sorbent, and a particle size of the
solid catalyst may be larger than a particle size of the solid sorbent.
[0022] The particle size of the solid catalyst may be equal to or larger than 150 microns,
and the particle size of the solid sorbent is less than 125 microns.
[0023] The system may further comprise a combustor for providing additional heat to the
calciner segment.
[0024] The solid sorbent may comprise lime particles.
[0025] The lime particles may be in the range of 20-200 microns and the temperatures at
the exhausts of the calciner and decarboniser segments are in the range of 700-950°C.
[0026] The system may further comprise a feed for feeding the output gas stream into a distribution
network.
[0027] The methane gas distribution system may comprise an existing NG distribution network.
[0028] The NG distribution network may comprise transportation of liquified gas and low
pressure gas delivery.
[0029] The gas distribution network may further be configured for delivering the output
fuel gas in the form of methane to a reactor configured for pre-combustion removal
of CO
2 from the methane.
[0030] The reactor configured for pre-combustion removal of CO
2 from the methane may generate separate Hydrogen and CO
2 streams from the methane.
[0031] The system may further comprising a feed for feeding the CO
2 gas stream into a CO
2 gas distribution network.
[0032] The CO
2 gas distribution network may be configured for delivery of the CO
2 gas stream for sequestration.
[0033] The CO
2 gas distribution network may be configured for receiving an additional feed from
an Endex reactor configured for pre-combustion removal of CO
2.
[0034] According to a second aspect of the present invention there is provided a method
for processing an input fuel gas and steam to produce separate CO
2 and output fuel gas streams, the method comprising the steps of using a decarboniser
segment for reacting at least a solid sorbent reacts with the fuel gas and steam to
remove carbon from the input fuel gas and to produce the output fuel gas stream in
an exhaust gas from the decarboniser; using a calciner segment for reacting the solid
sorbent from the decarboniser segment therein to release the CO
2 into the CO
2 gas stream; wherein CO
2 partial pressures and temperatures in the decarboniser and calciner segments respectively
are controlled such that the temperature in the decarboniser segment is higher than
the temperature in the calciner.
[0035] In the decarboniser, the steam may react with carbon monoxide in the fuel gas, or
produced from the fuels gas in the decarboniser, to produce CO
2 for adsorption by the solid sorbent.
[0036] In the decarboniser, the steam may react with hydrocarbons in the fuel gas to produce
either or both of the carbon monoxide and the CO
2.
[0037] The method may further comprise providing heat from the decarboniser to the calciner.
[0038] The output fuel gas stream may comprise hydrogen or methane.
[0039] The input fuel gas may comprise syngas, Hydrogas, SNG, or NG.
[0040] The method may further comprise providing a solid catalyst in the decarboniser segment
to activate a reaction to produce the output fuel gas in the exhaust gas from the
decarboniser.
[0041] The solid catalyst may comprise iron oxide.
[0042] A particle size of the solid catalyst may be larger than a particle size of the solid
sorbent.
[0043] The particle size of the solid catalyst may be equal to or larger than 150 microns
and the particle size of the solid sorbent is less than 125 microns.
[0044] The method may further comprise using a combustor for providing additional heat to
the calciner segment.
[0045] The solid sorbent may comprise lime particles.
[0046] The lime particles may be in the range of 20-200 microns and the temperatures at
the exhausts of the calciner and decarboniser segments are in the range of 700-950°C.
[0047] The method may further comprise feeding the output gas stream into a distribution
network.
[0048] The method may comprise transportation of liquified gas and low pressure gas delivery.
[0049] The method may further comprise delivering the output fuel gas stream in the form
of methane to a reactor configured for pre-combustion removal of CO
2 from the methane.
[0050] The method may further comprise using the reactor configured for pre-combustion removal
of CO
2 from the methane to generate separate Hydrogen and CO
2 streams from the methane.
[0051] The method may further comprise feeding the CO
2 gas stream into a CO
2 gas distribution network.
[0052] The method may further comprise using the gas distribution network for delivery of
the CO
2 gas stream for sequestration.
[0053] The method may further comprise receiving an additional feed for the CO
2 gas distribution network from the or an Endex reactor configured for pre-combustion
removal of CO
2.
BRIEF DESCRIPTION OF THE DRAWINGS
[0054] Embodiments of the invention will be better understood and readily apparent to one
of ordinary skill in the art from the following written description, by way of example
only, and in conjunction with the drawings, in which:
Figure 1 shows a schematic drawing illustrating generic process flows for a Flexible
Fuel Endex Reactor, according to an example embodiment.
Figure 2 shows a schematic drawing illustrating a process flow and reactor system
for a Flexible Fuel Endex reactor according to an example embodiment.
Figure 3 shows a schematic drawing illustrating an energy distribution network comprising
electrical power, NG/SNG pipelines and a CO2 network/pipelines with nodes being sources of NG/SNG and users of NG/SNG, sequestration
sites and NG/SNG sites, according to an example embodiment.
Figure 4 shows a schematic drawing of a process in which a number of Flexible Fuel
Endex reactors are deployed to (a) extract CO2 from a solid fuel to produce SNG a pure natural gas steam, (b) extract CO2 in a coal-to-methane generator at or near a mine site, or a biomass-to-methane generator
at or near a biomass source, and (c) extract CO2 from the natural gas/synthetic natural gas stream in the production of hydrogen for
low emissions industrial processes including the generation of energy, according to
an example embodiment.
Figure 5 is a schematic drawing showing another embodiment of a Flexible Fuel Endexreactor
for implementing the generic process flow of Figure 1 and for use in the energy distribution
network of Figure 3 and the process of Figure 4.
Figure 6 shows a flowchart illustrating a method for processing an input fuel gas
and steam to produce separate CO2 and output fuel gas streams, according to an example embodiment.
DETAILED DESCRIPTION
[0055] A Flexible Fuel Endex reactor decarbonises an input fuel gas stream into an output
fuel gas stream with a different composition of combustible gases and a carbon dioxide
gas stream. The generic process flows of a Flexible Fuel Endex reactor are shown in
Figure 1 for five configuration embodiments 10, 20, 30, 40 and 50. Embodiments 10,
20, 30 and 40 illustrate how a single reactor 110 can be configured for different
fuel streams and different product fuel streams, while embodiment 50 illustrates how
a pair of Flexible Fuel Endex reactors 120, 130 can be configured in series for additional
flexibility. These processes show the gas flows only, and do not include either the
ancillary systems or the inputs and outputs of solid sorbents or catalysts, as described
below. Also, the uses of various solid fuels such as coal of various ranks, biomass
or waste to produce the input Syngas or Hydrogas are not explicitly shown. It is noted
that a Flexible Fuel Endex reactor can advantageously operate with any of the inputs
as shown in embodiments 10, 20, 30 and 40 with a transition time between the input
fuels determined by the time to establish the new steady state in the Flexible Fuel
Endex reactor(s) (110, 120, 130). From the detailed description of an embodiment of
the Flexible Fuel Endex reactor, with the process flows shown in Figure 2, it will
be demonstrated that the Flexible Fuel Endex reactor acts as a gas switch. Further,
the Flexible Fuel Endex reactor is able to operate on a mixture of the fuel inputs
shown in embodiments 10, 20, 30 and 40, and can operate over a wide range of gas compositions
covered by Syngas, Hydrogas, NG and SNG. These fuel gas streams are characterised
by different amounts of methane, other hydrocarbons, hydrogen and carbon monoxide
as the combustible components, and steam, CO
2 and other inert components as the non-combustible components. The temperature, pressure
and compositions of these fuel gases depend on the method of their preparation. The
gas streams may, or may not, include sulphur and other undesirable gases. These minor
constituents are preferably be scrubbed from the input gases before injection. The
input pressure is preferably in the range of 15-40 bar and the input temperature is
preferably in the range of 400-900 C. For example, if input gas switching configurations
for the production of hydrogen are considered, it is preferable that the input gas
pressure is the same for both streams and the mass flow rates adjusted to give a constant
Calorific Value in the hydrogen gas stream. For applications as a fuel for power generation
using gas turbines, the Wobbe Index may also be adjusted by the excess steam in the
hydrogen gas stream.
[0056] The Flexible Fuel Endex reactor(s) (110, 120, 130) preferably generates any process
heat required for the chemical reactions that occur in the reactor by combustion of
either the input or the output fuel gas stream preferably with air. The process heat
includes that required for ancillary heat exchangers and possibly for the generation
of electricity from steam or gas turbines. The combustion of an input fuel gas for
process heat generates a flue gas with carbon emissions, whereas the combustion of
a decarbonised gas stream generates a smaller amount of carbon emissions. A hydrogen
gas stream combusts with negligible carbon emissions, associated with incomplete carbonation.
[0057] In embodiment 10 of Figure 1, the input fuel gas stream is Syngas 112 which may be
produced from a Partial Oxidation Gasifier, and the output is a hydrogen fuel gas
stream 116. In embodiments 20 and 30, the input fuel gas steam is Hydrogas 122, 132,
which is used to produce either a methane or a hydrogen fuel gas stream 126, 136 respectively.
[0058] In embodiment 40, the input fuel gas is NG or SNG 142 to produce a hydrogen fuel
gas stream 146. In each embodiment, steam 114, 124, 134, 144 is used to induce the
chemical reactions that produce CO
2 in the reactor, which is extracted as a CO
2 gas stream 118, 128, 138, 148. In embodiments 10, 30 and 40 the output gas stream
is a hydrogen gas stream, in which decarbonation is essentially complete (with a typical
90% capture efficiency), whereas in embodiment 20 the output fuel gas is methane 126,
in which case the decarbonation is typically about 45%. The details of these reactions
are considered below.
[0059] In embodiment 50, a pair of Flexible Fuel Endex reactors 120, 130 is used in series
to process Hydrogas 152 with the first reactor 120 producing a methane gas stream
156 with partial decarbonation, while the second reactor 130 produces a hydrogen fuel
gas stream 166, thereby completing the decarbonation. In this configuration, the output
may be methane 156 from the first reactor 120 and/or hydrogen fuel gas 166 from the
second reactor 130. By contrast, embodiments 20 and 30 use a single reactor to process
Hydrogas 122, 132 to either of these gas streams. The different outputs 126, 136 of
configurations 20 and 30 are controlled by the amount of the steam input, the presence
of different catalysts, and by the provision of external heat. The flexibility of
embodiment 50 is that the reactors can be physically separated, over hundreds of kilometres
with transport of methane being through an NG pipeline. It would be appreciated that,
in this case, the same gas would be unlikely to be used in the second reactor if the
pipeline was part of a NG distribution system. Rather, the process would work through
supply and outtake (indicated as NG stream 162) agreements with the NG pipeline operator,
for example with the requirement that the SNG input to the pipeline meets the same
specification as the input NG,
[0060] In order to accomplish the above processes of embodiments 10, 20, 30 and 40 in a
single reactor, each of the processes described above advantageously involve reactive
decarbonation. That is, the input fuel gas streams generally contain very little CO
2, and the CO
2 is produced from CO either in the input gas, as in a Syngas input, or produced by
steam reforming of methane as in a Hydrogas input. It is understood in the art that
the basic gas phase chemical reactions that enable such transformations leading to
decarbonation are active in the region of 600-900C, so that the CO
2 capture process preferably operates in this regime.
[0061] The primary reactions that occur in the reactors are the Water-Gas Shift reaction
(WGS) in embodiments 10, 20 and 50 (reactor 120), and the WGS and Steam Reforming
reactions (SR) in embodiments 30, 40 and 50 (reactor 130). These reactions are
CO +
H2O →
CO2 +
H2 Water Gas Shift
CH4 +
H2O →
CO + 3
H2 Steam Reforming
[0062] In the case of Hydrogas 122 and 132, NG and SNG 142 inputs, both reactions occur,
whereas in the case of Syngas 112 input, only the WGS reaction occurs. These reactions
occur at high temperatures in the range of 600-1000 C, generally in the presence of
a solid state catalyst.
[0063] Hydrocarbons in the fuel gas may also react with steam to form CO
2, e.g. with a stoichiometry of CH
4+2H
2O=CO
2+4H
2. That is, the steam can react with hydrocarbons in the fuel gas to produce either
or both of carbon monoxide and CO
2.
[0064] These reactions do not separate the CO
2, but that separation is accomplished by the injection of a CO
2 sorbent, such as lime (CaO) or dolime (CaO.MgO), which extract the CO
2 as a solid carbonate, for example as calcium carbonate CaCO
3. The net effect is that the adsorption of CO
2 by the solid CaO particles enhances the formation of hydrogen through shifting the
equilibrium of both the WGS and SR reactions according to LeChatalier's principle
through the gas decarbonation reaction, which, in the case of lime as a sorbent, is
CaO(
s) +
CO2 →
CaCO2(
s)
Gas Decarbonasation
[0065] The net reactions are
CO +
H2O +
CaO(
s) →
CaCO2(
s) +
H2Sorbent Enhanced Water Gas Shift
CH4 + 2
H2O +
CaO(
s) →
CaCO2(
s) + 4
H2 Sorbent Enhanced Steam Reforming
[0066] The Sorbent Enhanced WGS process, SEWGS, has been described by
S.Y.Lin, M.Harada, Y.Suzuki and H.Hatano, "CO2 separation during hydrocarbon gasification",
Energy, 30, 2186-2193 (2005) and
S.Y.Lin, M.Harada, Y.Suzuki and H.Hatano, "Process analysis for hydrogen production
by Reaction Integrated Novel Gasification (HyPr-RING)", Energy Conversion and Management,
46, 869-880 (2005). The SEWGS process with hydrotalcites is described by
P.D.Cobden, "High Capacity Hydrotalcites" IEA Solid Network Looping Conference in
Oviedo Sept 2009.The Sorbent Enhanced SR reaction, SESR, is described by
Balasubramanian, B.; Ortiz, A.L.; Kaytakoglu, S.; Harrison., D.P. "Hydrogen from methanein
a single-step process", Chem. Eng. Science, 1999, 54, 3543-3552 and
Ding,Y.; Alpay, E. "Adsorption-enhanced steam-reforming", Chem. Eng. Science,2000,
55, 3461-3474.While the SESR and SEWGS reactions are well understood, the conditions for their
application to flexible decarbonation as described herein has not previously been
described. Conventional carbon capture systems, such as amine or proprietary solvent
technologies, cannot operate in this temperature regime and are intolerant to the
reactive species in fuel gas streams at these temperatures.
[0067] Minor hydrocarbon constituents in the fuel gas may be also be reformed by steam to
hydrogen and carbon dioxide. Steam reforming of methane initially produces carbon
monoxide, which is then transformed to carbon dioxide and additional hydrogen by the
WGS reaction. In Sorbent Enhanced WGS (SEWGS) and Sorbent Enhanced SR (SESR), decarbonation
of the gas causes the WGS and SR reactions to produce additional hydrogen, thereby
driving the reactions to completion. The thermodynamics of these reactions are understood,
with the WGS reaction being slightly exothermic with a heat of reaction -41.2 kJ mol
-1, the SR reaction being strongly endothermic with 165.0 kJ mol
-1, and the decarbonation reaction being strongly exothermic with -179.6 kJ mol
-1. The kinetics of these reactions are understood, and both the WGS reaction and the
SR reactions are generally too slow below 1000 C, and are catalysed by a solid catalyst.
At temperatures of about 850 C, the catalyst most after used is a mixed valence iron
oxide, which is known to catalyse both reactions. In most WGS reactor designs, the
iron oxide sinters and its catalytic activity is lost. Low temperature WGS reactors
use a more powerful catalyst such a nickel. In commercial WGS and SR reactors, the
catalyst is held in the reactors by being supported on various substrates that remain
in the reactor.
[0068] The introduction of lime, CaO, as a sorbent for the SEWGS and SESR reactors in the
desired range of 600-900 C, has been studied. The sorbent, when loaded with CaCO
3, is transported to a Calciner reactor in which the sorbent, CaO is regenerated and
the CO
2 is released as a pure gas stream, which is cooled and compressed, through the calcination
reaction
CaCO3 →
CaO(
s) +
CO2 Calcination
[0069] The overall process of cycling the sorbent between a Gas Decarbonation (or Sorbent
Carbonation) reactor and a Calcination reactor is called Calcium Looping or Calcium
Oxide Looping initially described by
Temminck and Heesink(PCT WO94/01203 4994) for
CO2 capture from flue gas, and
CO2 capture from a Water Gas Shift reactor for a fuel gas.
[0070] The major impediment to the SEWGS process at about 850 C is associated with three
fundamental properties of the CaO sorbent, namely the sintering of the CaO particles
at these temperatures and pressures, the attrition of the CaO particles, and the irreversible
reaction of CaO with volatile sulphur compounds, if present, such as H
2S and COS to form CaS, and the reaction with volatile chlorides, if present, to produce
CaCl
2. The sintering occurs by thermal sintering catalysed by both CO
2 and H
2O above 900 C, and reactive sintering above about 10% sorbent carbonation. If the
rate at which the sorbent has to be replenished is very high, as result of cumulative
formation of CaS, sintering or attrition, then there is an energy penalty because
the CaO sorbent is first manufactured by calcination of limestone, CaCO
3. This production process consumes energy and produces CO
2. The Zero Emissions Coal process (
J.. Ruby, A. Johnson, H. Ziock and K. Lackner, Proceedings of 21st International Technical
Conference on Coal Utilization and Fuel Systems, Clearwater, Florida, 4-7, March 767
(2002)) considers the production of methane using lime, but an efficient means of separating
the
CO2 was not established.
[0071] Sceats, in "System and method for Processing Flue Gas" (
PCT/AU2009/000613) describes an efficient means of CO
2 separation for flue gas. That work describes a configuration of sorbent Carbonation
and Calcination reactors, called.the Endex configuration, in which the CO
2 separation can be achieved with negligible additional energy. This is achieved by
thermally coupling the reactors so that they operate as a coupled pair with one reactor
operating exothermically (the Carboniser) and the other operating endothermically
under steady state conditions in which the heat from the exothermic reactor flows
spontaneously to the endothermic reactor. By controlling the CO
2 exhaust pressure the temperature of the Calciner is set to be lower than that of
the Carboniser, such that this condition is achieved. An advantage of the Endex configuration
is that the thermal sintering of CaO is minimised by the low calcination temperature
and the reactive sintering is minimised by the ability to operate the reactors efficiently
with a low degree of carbonation. The heat transfer occurs through the walls of the
reactor, or sorbent transfer or a combination of both. Thus both the sorbent and the
energy are recycled in the reactor system. For CO
2 separation from flue gas, the energy for sorbent carbonation is equal to the energy
of calcination, so that preferably no additional energy is required, other than for
parasitic energy losses, such as radiative heat loss..
[0072] The example system and method embodiments herein describe the application of Endex
principles to the decarbonation of fuel gas streams to produce a decarbonated, or
partly decarbonated, fuel gas steam and a compressed CO
2stream from the Flexible Fuel Endexreactor. The embodiments of Figure 1 each use a
high temperature CO
2 sorbent looping to achieve the decarbonisation of the fuel gas. The sorbent is generally
limestone, although other high temperature looping sorbents such as dolime CaO.MgO
may be used. The embodiments also include catalysis of the reactions, which may be
accomplished by iron oxide or other catalysts, in either the form of particles that
are looped with the CO
2 sorbent, or as supported catalysts that are held/supported in the reactor where the
catalyst is required. Limestone can be found that comprises CaCO
3 and Iron Oxide as constituents in the ground particles, so the sorbent lime particles
contain the catalyst in one embodiment. Or, if the lime sorbent is made in a process
such as from a precipitate of Ca(OH)
2, then the catalyst can be added at that stage. That is, the solid catalyst can be
supported in the decarboniser reactor, or mixed with the solid sorbent as separate
particles, or incorporated into the solid sorbent. In embodiments using lime particles
as the solid sorbent, the particles are preferably in the range of about 20-200 microns
and the temperatures at the exhausts of the calciner and decarboniser are in the range
of about 700-950°C.
[0073] The Flexible Fuel Endex reactor in example embodiment comprises in general three
segments. The first segment is the Gas Decarboniser that decarbonises the input gas
stream using the SEWGS or SESR reactions with a high temperature sorbent and which,
through control of the coupling to the other segments and the steam content of the
input gas stream, regulates the reaction of the fuel gas inputs to produce the required
amounts of the fuel gas and CO
2-loaded solid sorbent streams. This reactor contains the catalyst, either supported
and retained in the reactor, or transported with the CO
2 sorbent. The second segment is the Calciner that regenerates the sorbent and produces
the CO
2 gas stream for compression and sequestration. The pressure of the CO
2 gas stream is used to control the extent of decarbonation in the Gas Decarboniser
and is a preferably the means of controlling the extent of carbonation.The third segment
is the Combustor which combusts a fuel to generate the process heat that is supplied
to the Gas Decarboniser and the Calciner in proportions to control the operation of
the reactor. These three reactor segments are coupled thermally so that heat can flow
between them. The heat may flow through the common walls of the reactors, or may be
transferred between the reactors, with the latter mechanism being able to regulate
the amount of heat transfer and control the extent of the reactions in the Gas Decarboniser
and Calciner segments as required. The temperature rise in the Gas Decarbonation reactor
is preferably suppressed by the heat loss to the Calciner, where the temperature drop
is also limited. In this invention, the application of the Endex reactor is extended
to the case for fuel gases in which there is one or more chemical reaction of the
fuel gas in the Gas Decarboniser segment of the Endex reactor. This configuration
is called the Flexible Fuel Endex reactor herein. In the specific case of interest,
the predominant chemical reactions are the WGS reaction of CO with steam, and the
SR reaction of methane with steam.
[0074] The presence of the chemical reactions generally requires process heat, which is
explicitly provided in regulated amounts from a separate Combustor segment, explicitly
as a means of controlling the desired reactions. In the Endex reactor, the CO
2 separation from flue gases is controlled through regulation of the CO
2 exhaust gas pressure for constant inputs. In the Flexible Fuel Endex reactor, the
chemical composition of the fuel gas output stream and the extent of carbon capture
through regulation of the CO
2 exhaust gas pressure as well as the steam input, and the heat transfers from the
Combustor segment to each of the Gas Decarboniser and Calciner segments, control the
CO
2 separation.
[0075] Figure 2 shows a WGS Flexible Fuel Endex reactor 200 embodiment in which the heat
is transferred between three reactor segments, the Gas Decarboniser 201, the Calciner
202 and the Combustor 203. The inputs to the reactor are Syngas 206, Hydrogas 208
and NG/SNG 210. These are the input fuel gas stream options considered in Figure 1.
The input can be selected by a gas valve system 212 which can be used to select or
mix the fuel gas streams, taking account of the temperature and pressure of each of
the input gas streams. The resultant gas stream 214 is injected into the Gas Decarboniser
segment 201 along with steam 216. The mass flow rates, temperature, pressure and heat
exchanges into this segment are used to control the extent of the SEWGS and SR reactions.
For example, the SESR reaction is slightly exothermic with a heat of reaction of -14.6
kJ mol
-1 so that the heat generated is relatively small to achieve equilibrium. On the other
hand, the SEWGS reaction is highly exothermic with a heat of reaction of-220.8 kJ
mol
-1 so that the heat generated is relatively large. Some of the heat generated can be
used to heat the input gas streams 214 and 216. The means of controlling the heat
transfers to give the desired output fuel gas stream 218 is considered below.
[0076] The steam input 216 is generated by heating water 220 in a boiler 222, which requires
process heat 224. The sorbent input 226 to reactor 201 comprises a flow 228 from the
Calciner 202 segment. There may be an heat transfer 230 through the walls between
the Gas Decarboniser 201 and the Calciner 202 segments and a heat transfer (not shown)
between the Gas Decarboniser 201 and Combustor 203 segments. The direction of the
former heat flow is determined by the overall Flexible FuelEndex reactor 200 steady
state, whereas the combustor 203 will generally be at a higher temperature than either
of the other reactor segments 201, 202. The sorbent exhaust 232, now loaded with CO
2 is transferred 234 to the Calciner 202 segment for regeneration. The fuel gas output
218 is cooled in a Gas Cooler 236 and heat 238 is extracted as required for the specified
application of the flue gas stream 240. In some applications, the hot pressurised
output flue gas stream 240 is directly injected into an industrial process, for example,
for the production of electrical power. In other applications, the hydrocarbon and
hydrogen components are separated in the hydrogen separator 242 to yield a hydrogen
rich gas stream 244 and a methane rich gas stream 246 (i.e. essentially SNG). Any
excess steam in the output 240 may be condensed from the gas stream 240 as water (not
shown), and recycled. The hydrogen rich gas stream 244 may be separated by a valve
248 into two streams, a product stream 250 and a process fuel gas stream 252 for combustion,
if required, in the Combustor segment 203.
[0077] In the Calciner segment 202, a solids feed 254 of fresh limestone particles and a
catalyst is introduced to replenish the sorbent and catalyst. In this embodiment,
the catalyst may be disposable, low cost iron oxide particles. In other embodiments,
the catalyst may be supported in the reactor or may be found as desirable components
in the mineral limestone feed. In the case of SEWGS, both CaO and MgO are understood
to act as catalysts in the temperature regime of interest. The Calciner reaction is
endothermic and requires +179.6 kJ mol
-1 of heat independently of whether the CO
2 was generated SEWGS or SESR net reactions. This heat is primarily obtained by heat
transfer from the Gas Decarboniser 201 for SEWGS or the Combustor 203 for SESR. This
heat is obtained from the wall heat transfers 230, 258, and the sorbent flows 228,
254, 256, 234, 260 and 262. The spent sorbent/catalyst 262 is exhausted from the Calciner
202, and heat may be extracted from this stream and used to preheat the input sorbent/catalyst
254. The major control parameters of the system 200 are (a) the setting of the pressure
of CO
2 in the Calciner 202 exhaust, (b) the control of the thermal energy released in the
Combustor 203 and (c) the mass flow rates of the sorbent between each of the reactors.
The CO
2 product stream 264 is cooled in a Gas Cooler 266 with the liberation of heat 268
and the cooled CO
2 stream 270 is compressed in a compressor system 272 to give a compressed CO
2 fluid stream 274 appropriate for transport and sequestration through the application
of power 276.
[0078] The Combustor segment 203 uses either the hydrogen slip stream 252 or an alternative
fuel 278, which may be the one of the input fuel gas streams of Syngas 206, Hydrogas
208, NG or SNG 210, to produce the process heat required. The use of hydrogen for
combustion in air 280 generates a low carbon emissions flue 290, whereas the use of
one of the other input streams produces a flue gas with significant CO
2. For the SEWGS reactions, the amount of heat required from Combustor 203 is small
and arises from heat losses and the like, whereas for the SESR reaction considerable
process heat is used to ensure that the endothermic Calciner's 202 thermal energy
requirement of +179.6 kJ mol
-1 is met principally through heat transfer from the Combustor 203, whereas in the SEWGS
reactor the Calciner 202 operates principally through heat transfer from the Gas Decarboniser
201. On this basis, it is evident that the spontaneous heat transfers will occur for
both reactions when the Calciner 202 is at the lowest temperature. This is one differentiating
feature of the Flexible FuelEndex configuration compared to other SESR and SEWGS reactor
processes where the Calciner is at a higher temperature than the Gas Decarboniser.
In such prior art, heat is generated by combustion within the Calciner of a fuel with
oxygen to ensure that the exhaust gas is primarily CO
2 and steam. Oxygen generation is an expensive process. In the example embodiment,
efficient thermal coupling of the reactors advantageously leads to an efficient decarbonation
process. The design of the reactor 200 preferably takes account efficient heat transfer
from the Calciner 202 segment to both the Gas Decarboniser 201 segment and the Combustor
203 segment. In order to scale the size of the reactors, it is preferable that the
heat is transferred primarily by the sorbent.
[0079] Because the Gas Decarboniser 201 segment is at high pressure, there are mechanical
design benefits if the Combustor 203 also operates at the high pressures of the Gas
Decarboniser 201. In such an embodiment, the additional benefit of using high pressure
combustion is that electrical power can be generated. The air input 280 is compressed
by the compressor 282 with consumption of electrical power 284, heated in the Combustor
203 to give a hot flue gas 286 which is expanded in the turboexpander 288 to generate
electrical power 290. Sufficient fuel can be combusted so that the electrical output
290 from expansion can meet the power demands of the air compressor 284 and the CO
2 compressor 276, and any other ancillaries used in the system 201, such as required
for solids handling through pneumatic transport and lockhoppers. The heat transfer
from the Combustor 203 segment to the Calciner 202 segment can be controlled by the
transport of an amount of sorbent through the Combustor 203 from the Calciner 202
at 260, with the heated sorbent exhaust at 292 being recirculated into the Calciner
202 at 256. The flue gas 294 may be further cooled to extract heat for recuperation.
[0080] The degree of carbonation of the sorbent can advantageously be reduced to about 6%
by using a high solids flow so that the effects of reactive sintering are reduced.
The reduction of the temperature variation by such heat transfer means that the thermal
sintering of the sorbent is reduced. However, the sorbent is typically still subject
to attrition and sulphidation, and may be replenished periodically.
[0081] In the Flexible Fuel Endex reactor 200 of Figure 2 embodying the present invention,
the sorbent, and the catalyst if required, are recycled and the gas flows are continuous.
Continuous flow reactors may be preferable in a production system. Continuous flow
may also be preferable in the case in which the resultant fuel, e.g. hydrogen, is
consumed continuously, for example, in a combustion process where flames are susceptible
to variations in gas flow. It is recognised that ballast tanks and valves can be used
to smooth the gas flow in such systems. The advantages of a sorbent flow system include
that attrition is preferably removed as an issue, and the sorbent and catalyst replacement
to make up for both sintering and sulphidation can be simply achieved by bleeding
the materials in and out from the reactor. For the application in this embodiment,
it has been recognised by the inventors that the majority of the input gas mass of
steam and the fuel gas is captured by the sorbent as CaCO
3, and the low mass of the hydrogen gas left behind cannot lift the sorbent through
the Gas Decarboniser. Therefore, the Flexible Fuel Endex reactor 200 shown in Figure
2 is comprised of three downer segments 201, 202, and 203 with pneumatic transport
by a hot gas used to lift the particle streams from each of the bases of the segments
201, 202 and 203 for injection into the throats of the receiver reactors.
[0082] The Flexible Fuel Endex system, such as that shown in Figure 2, processes any of
the input fuel gas streams, such as 206, 208, 210, or mixtures thereof, to produce
the required output fuel gas streams such as 246, 250 and the CO
2 stream 274. If the input gas stream contains no methane then no methane would be
produced, and if SNG or NG is a pure input, then the system operating conditions would
logically preferably be controlled to consume the SNG/NG, so the methane output would
be set to be negligible. That is, the operating conditions would be set by the controls
described above to achieve one of the outcomes shown in Figure 1.
[0083] In the Flexible Fuel Endex configuration, the need for external energy input is also
advantageously minimised by organising the temperature of the Calciner 202 exhaust
to be lower than the temperature of the Gas Decarboniser 201 exhaust so that heat
spontaneously flows from the Gas Decarboniser 201 to the Calciner 202, and the energy
is recycled. This can be achieved by controlling the CO
2 partial pressure. Similarly, In the Flexible Fuel Endex configuration, the Combustor
203 temperature is preferably set such that it is also higher than that of the Calciner
202 so that heat spontaneously flows from the Combustor 203 to the Calciner 202. This
can be achieved by controlling the fuel gas 252 or 278 to air 280 mass flows. These
heat flows spontaneously transfer energy from the hotter Gas Decarboniser 201 and
Combustor 203 segments to the cooler Calciner 202 by both the wall heat transfer and
the sorbent/catalyst heat transfer. If the sorbent flow rate can be made sufficiently
high, then the reactors can be configured so that no heatflows through the walls are
required. This means that the catalyst solids do not have to be supported in the reactor,
but can move through the reactor entrained with the sorbent solids. The ability to
readily replace the catalyst means that advantageously iron oxide particles, direct
from a mine or as an impurity in the limestone if appropriate, can be used, therefore
advantageously by passing the need to pre-process the iron oxide with CaO. That is,
both the CaO and iron oxide can be readily replaced if both are present as particles
that are cycled between the two reactor segments.
[0084] It is preferable that the CaO sorbent particles are less than about 125 microns so
that the calcination-carbonation reaction occurs uniformly within the particle at
a fast rate that is not inhibited by gas and thermal transport. The catalyst particles
may e.g. be in the range of 150-250 microns so that the sorbent and catalyst solids
streams can be separated from the spent solids if required. A further advantage of
the high solids flow is that only partial carbonation is required, and if this is
kept to less than about 6% to minimise reactive sintering, each particle can preferably
act as its own heat bath as it is transported between the reactor segments 201, 202
and the heat transfer through the walls can be minimised. Minimising the wall heat
transfer can facilitate the scaling of the reactors to large systems. In the Flexible
Fuel Endex reactor 200 in Figure 2, the fast heat exchange between the particles is
preferably such that the solid catalyst particles contribute to the heat transfer,
and can facilitate the heat transfer between the reactor segments 201, 202 and 203.
[0085] The processing of the sorbent through the Combustor segment 203 has a number of secondary
benefits. Firstly, the combustion can remove any carbon built up from the Boudouard
side reaction on the sorbent and catalyst particles in the Gas Decarboniser segment
201, which may otherwise accumulate and impede the respective calcination/carbonation,
WGS and SE reactions on the particle surfaces. Secondly, the Combustor 203 provides
an oxidising environment whereas the Gas Decarboniser 201 is a reducing environment,
so that the iron oxide catalyst can preferably be maintained in the mixed valence
state oxidation state FeO.Fe
2O
3 of magnetite responsible for catalytic activity, by controlling the residence times
in the respective reactors. It is noted that magnetite often occurs as an impurity
mineral in limestone deposits, and with the preferable high solids loading in the
Gas Decarboniser 200 the required catalytic activity may be obtained without the need
to add separate magnetite particles. Should magnetite be added separately, residual
magnetite particles may be separated from the spent sorbent stream by their magnetic
properties and re-injected into the fresh sorbent stream.
[0086] The amount of fuel gas that is consumed in the Combustor 203 preferably provides
sufficient heat for the chemical processes and to make up for the temperature losses
of the Flexible Fuel Endex reactor 200 from parasitic radiative and conductive losses.
The increase of the temperature of the sorbent particles in the Calciner 202 from
the Combustor 203 heat is such that the temperature of the CO
2 in the Calciner 202 is increased, and the partial pressure of CO
2 is increased. The benefit of a higher CO
2 partial pressure is that the energy required to pump the CO
2 from the Calciner 202 is lowered.
[0087] The ability in preferred embodiments to continuously extract CO
2 from the fuel gas stream with minimal input of energy, while retaining the temperature
of the primary gas stream at close to the optimum, is very significant for pre-combustion
carbon capture not only because the net energy penalty is very small, but also because
the gas can be made available continuously at high temperature and pressure for combustion
in an Combined Cycle (CC) process to produce electricity. The Flexible Fuel Endex
reactor allows for pre-combustion carbon capture for the Integrated Gasification Combined
Cycle (IGCC) process for power generation in which Syngas is generally considered
as the source of fuel gas from the solid fuel, although Hydrogas could be equally
used to produce the fuel gas. The Flexible Fuel Endex reactor allows for pre-combustion
carbon capture for the Natural Gas Combined Cycle (NGCC) process for power generation
in which fuel gas is NG or SNG. This demonstrates the flexibility of the Flexible
Fuel Endex reactor. From the perspective of an operator of a Gas Turbine system, the
Flexible Fuel Endex reactor allows the Gas Turbine to be used with a variety of fuel
sources, from coal to NG. Thus the large capital cost for a power plant is preferably
not locked into a particular choice of fuels for the 20-30 year operating period of
the plant.
[0088] The integration of a Flexible Fuel Endex reactor embodying the present invention
into an IGCC stream is based on the observation that the hydrogen gas stream 250 in
Figure 2 is (a) at a high pressure required for gas turbines in the range of 30-40
bar; and (b) and the high temperature of the gas carries high thermal energy that
is not required to be provided for by the gas turbine combustion and (c) the steam
and inert gas content of the hydrogen gas stream are beneficial in the efficiency
of the Gas Turbine. Because the energy in the input hydrogen gas stream has been generated
by the low temperature processes in the Flexible Fuel Endex reactor, the amount of
NO
x generated in the Gas Turbine is considerably reduced. The expenditure of energy in
the Combustor 203 is offset by the heat in the hydrogen gas stream, such that overall,
there is negligible thermal efficiency loss in the overall electrical energy generated
in the IGCC/NGCC process.
[0089] In one embodiment, lime (
CaO) preferably produced from limestone (
CaCO3) is used as the inorganic salt which acts as a catalyst for various processes described
herein, and as a
CO2 sorbent. In other embodiments, other materials such as magnesium oxide (MgO), dolime
(
MgO.CaO) or semidolime (
MgO.CaCO3) produced from magnesite or dolomite may be used. Other materials include catalysts
such as potassium carbonate, sodium carbonate, ferrous nitrate, nickel (II) nitrate
and ferrous sulphate.
[0090] Sceats and Horely (
PCT/AU2007/000424), describe a flash calciner in which steam is used to catalyse the production of
CaO from
CaCO3, and that process may be adopted for the production of
CaO for this application by separating the
CO2 from the steam by water condensation. In another embodiment, the
CaO can be produced in a conventional kiln, with the
CO2 emissions from both the calcination and the combustion contributing to the carbon
footprint of the overall process. The
CaO production process preferably produces
CaO with a high surface area to give fast reaction kinetics with CO
2 in the Flexible Fuel Endex reactor.
[0091] The spent sorbent/catalyst stream 262 contains primarily lime CaO. It is understood
that lime can be injected into either a Hydrogasifier or a Partial Oxidising Gasifier
to extract sulphur as CaS from the Hydrogas and Syngas streams. In respect of Hydrogas,
the lime may have an additional benefit through its impact as a catalyst for hydrogenation
of solid fuels.
[0092] In the following, embodiments of an energy generation network that utilize the natural
gas distribution network are described to deliver fuel, as substantially methane,
to power generation systems in which efficient CO
2 capture is carried out firstly at the source of generation of the methane from gasification
of coal or biomass at or near the sources of these respective solids feedstock, or
from the natural gas at or near the well head, and secondly at the source of generation
of electrical power or other industrial process, so that a low CO
2 emissions process for energy use is established.
[0093] Referring to Figure 3, an energy network 300 is comprised of an electrical power
transmission and distribution network 301, a compressed NG pipeline network 302, which
includes transportation of NG as Liquefied Natural Gas, and the low pressure delivery
of natural gas to customers, and a carbon dioxide (CO
2) distribution network/pipeline 303, which may initially occur through the use of
road tankers, barges or ships carrying compressed CO
2 or dry ice, which is solid CO
2. The roll out of pipelines for CO
2, is expected to occur where practicable as the demand for CO
2 capture and sequestration develops.
[0094] The NG network/pipeline 302 can be used to transport SNG provided that the specification
for the composition and calorific value of SNG meets that of NG. The NG network 302
is fed from one or more NG sources 304 and the NG is delivered to one or more power
plants 305, such as NG, NGCC or CHP gas turbine generators and industrial processing
plants 306, which can include e.g. cement and iron and steel plants. Generally, the
NG sources 304 are found in remote locations, whereas the power plants 305 and industrial
processes 306 are located in or near metropolitan areas, to access people and in the
case of electricity, preferably, to reduce power transmissions losses.
[0095] This NG network 302 can be supplied from SNG produced by, for example, hydrogasification
of coal 307 or biomass 308. The coal in this context refers to any non-gaseous fossil
fuels such as coal of various ranks, including lignite or peat, tar sands and oil
shale. The hydrogasifiers for coal, tar sands or oil shale may be industrial plants,
or the hydrogasification process may be carried out underground or undersea in the
fossil fuel deposits. CO
2 is generated from a number of sources; from natural gas itself which contains CO
2 as an impurity; from the hydrogasification of coals and biomass; from industrial
processes such as cement, lime, iron and steel, power generation and residential consumers.
Generally, CO
2 capture from residential consumers is not viable. The CO
2 emissions from each of the other aforementioned users is of such a magnitude that
they are expected to be subject to increasing regulations, taxes and permits in order
to reduce mankind's CO
2 emissions.
[0096] An advantage of the energy network 300 is that the SNG/NG can be stored in large
underground reservoirs 310, so the electrical power can be generated on demand without
the requirement to turn down any SNG production plant. The NG/SNG reservoirs can advantageously
be an important consideration for energy security.
[0097] Another feature of the energy network 300 described is that a medium to low calorific
value fuel such as coal is preferably converted to a high calorific value fuel such
as SNG at the site where the fuel is located, such as coal fields and biomass plantations.
In the process described, about 50% of the carbon from the coal is captured as CO
2, and the remainder, predominantly in the form of methane, is transmitted as SNG to
industrial or metropolitan centres via the NG/SNG network 302, where the remaining
50% of carbon can be captured. If each process has e.g. a 90% capture efficiency,
then about 45% of the CO
2 capture occurs at the NG/SNG processing sites (104, 107, 108) and about 45% is captured
in the end users sites. Each NG/SNG generator and each NG/SNG end user has, in principle,
the opportunity of transmitting the separated CO
2 through the CO
2 transport network 303 for sequestration.
[0098] The enabling technology for the energy network 300 in an example embodiment shown
in Figure 3 is a CO
2 separation technology that has a high CO
2capture efficiency which is affordable. Generally, CO
2 capture is preferably performed under high gas pressures as this typically lowers
the cost because the smaller volumetric flow rates means a lower physical footprint,
and because any CO
2 separation process will have a higher efficiency if the CO
2 is at a higher pressure than that produced in conventional atmospheric combustion
systems. The energy network 300 employs pre-combustion CO
2 capture systems in which the CO
2 is extracted from the fuel source in two stages, firstly by the NG/SNG generator
and secondly by the NG/SNG end user. The flexibility of the energy network 300 includes
the ability to turn on or off the CO
2 capture processes to meet the demands and regulations. In most existing CO
2 capture technologies, the energy loss associated with the CO
2 capture plant is such that it would be preferable to bypass the CO
2 capture units, and turn them off if the demand or price for CO
2 was too low. However, the stability of large scale processing plants is such that
they are difficult to ramp and down, and this process can take hours to days.
[0099] On the other hand, the Flexible Fuel Endex reactor, including as described above
with reference to Figures 1 and 2, have a sufficiently low thermal energy penalty
such that there is no advantage in turning off the CO
2 separation process if the demand or price for CO
2 was too low. Rather, the CO
2 can be advantageously stored locally for later transmission for sequestration, or
can be vented, or otherwise deployed in other industrial processes.
[0100] The energy network 300 preferably has the following features:-
- a. The capture system for the removal of CO2 for the NG/SNG production should be able to be operated at any level of the turndown
of the NG/SNG production process, and is not the determining factor in the ramp up/ramp
down of the NG/SNG production process., The penalty for CO2 capture in this process is low so that the production of NG/SNG is decoupled from
the economics of carbon sequestration.
- b. The end user capture system for the removal of CO2 from, e.g. the power generation system operates with a small energy penalty such
that its output would be used in the gas turbine power unit independently of whether
or not CO2 capture was required for regulatory or financial reasons. That is, if CO2 sequestration is not warranted or required, the only operational decision to be made
is whether or not to vent the CO2. In general, it is not possible to run a gas turbine optimally with any fuel and
a turbine is generally optimised and run on a single fuel composition. This is set,
for example, by the Wobbe Index of the fuel. While multiburner gas turbine systems
may obviate this necessity, it is preferable that the gas composition is maintained
independently of the need for hydrogen production.
[0101] In Figure 4, the use of the Flexible Fuel Endex reactors in the energy network 400
are shown explicitly in the three roles in a system where the three networks for power
401, NG/SNG 402 and CO
2403 are shown. In the first Flexible Fuel Endex reactor 404, an input stream of NG,
405, from a well-head source is injected into the reactor which separates the CO
2406 from the methane 407, and each gas stream is injected into the respective pipeline
403, 402 respectively. The steam content of the well head gas is preferably low or
the fuel is dried, so that the steam reforming reaction is quenched such that the
methane in the gas stream is not converted to hydrogen. Nevertheless, a small amount
of hydrogen preferably ensures that carbon deposits are not formed in the reactor.
In this first Endex reactor 404, the lime sorbent (not shown) extracts the CO
2 from the gas stream. It would be appreciated by a person skilled in the art that
the lime also preferably removes sulphur through sulphidation to form CaS, which can
be later oxidised to form gypsum.
[0102] The second Flexible Fuel Endex reactor 408 is used to drive the generation of hydrogen
from methane for the gasification of coal or biomass feedstock 409 in the hydrogasifier
unit 410. The hydrogasifier 410 produces a gas stream 411 which is substantially methane.
A part of this gas stream 412 in injected into the Flexible Fuel Endex reactor 408
with steam 413 so that the steam reforming reaction generates sufficient hydrogen
414 for the hydrogasifier. The other part of the methane gas stream 415 is injected
into the NG/SNG pipeline 402, and the CO
2 stream 416 from the Flexible Fuel Endex reactor is injected into the CO
2 network/pipeline 403. It would be appreciated by a person skilled in the art that
the lime (not shown) in the Flexible Fuel Endex reactor also preferably captures sulphur
from the output of the gasifier. The spent CaO sorbent can be used in a guard bed
so remove the sulphur from the methane gas stream 415.
[0103] The first two Endex reactors 404, 408 demonstrate that CO
2 removal from NG, coal, tar sands, oil share or biomass can be accomplished in the
production of methane. In the first case, the CO
2 is removed as an impurity in the gas stream as a part of the gas clean-up process,
while in the second case the CO
2 is removed in the conversion of coal or biomass to methane. Typically this means
that the Endex reactor operating with an efficiency of about 90%, will remove about
45% of the carbon in the feedstock, with the remainder of the carbon being in the
methane gas. In Figure 4, the methane from these two sources is injected into the
NG/SNG pipeline 402. The NG/SNG is extracted by an end user as an energy source. The
combustion of methane advantageously produces about 50% less CO
2 for the same thermal energy than coal or biomass, depending on the composition of
the feedstock. The system 400 preferably lowers the emissions by 45% or more from
the use of the feedstock as a fuel.
[0104] Notwithstanding this benefit, users of NG/SNG will be under regulatory pressure to
reduce their CO
2 emissions. Post combustion capture of CO
2 from gas turbines is generally too difficult because of the very low partial pressure
of CO
2 in the gas turbine exhaust. However, the third Flexible Fuel Endex reactor 422 shown
in Figure 4 illustrates that the CO
2 can be captured by reacting the methane stream 420 with steam 421 to produce hydrogen
423 which is used as the fuel for a gas turbine 424 on hydrogen to produce power 425,
which is transported into the electrical grid 401. The CO
2 stream 426 from the Flexible Fuel Endex reactor is injected into the CO
2 network/pipeline 403 for sequestration.
[0105] Figure 5 is a schematic drawing showing another embodiment of a Flexible Fuel Endex
reactor 500 for implementing the generic process flow of Figure 1 and for use in the
energy distribution network of Figure 3 and the process of Figure 4. More particularly,
the Flexible FuelEndex reactor 500 is based on gas switching. In this example embodiment,
a fuel gas and steam input stream 501 is provided to an entrance of switchable Decarboniser
and Calciner segments 510, 506 of a reactor system 502. In the Decarboniser segment
510, 506, either the WGS or the SR reactions proceed depending on the fuel gas and
the heat transfers between the segments 510, 506 and a combustion source (not shown).
[0106] In a first switching configuration, an entry valve 504 into the first segment 506
of is in an open position, whereas an entry valve 508 into the second segment 510
is in a closed position. Similarly, an exit valve 512 of the first segment 506 is
in an open position, while an exit valve 514 of the second segment 510 is in a closed
position. Additionally, a CO
2 exhaust valve 516 of the first segment 506 is in a closed position, while a CO
2 exhaust valve 518 of the second segment 510 is in an open position. In this switching
configuration, the first segment 506 functions as a decarboniser reactor for a first
portion 520 of a solid sorbent and solid catalyst 520 disposed in the first segment
506 of the Flexible Fuel Endex reactor 500, while the second segment 510 functions
as a calciner for a second portion 522 of a solid sorbent and solid catalyst 520 disposed
inside the second segment 510.
[0107] It will be appreciated by a person skilled in the art that by periodically changing
the switching configuration to reverse all of the valve positions in Figure 5, the
first and second segments 506, 510 of the Flexible Fuel Endex reactor 500 can function
as either a decarboniser or a calciner for the respective first and second portions
520, 522 of solid sorbent and solid catalyst. It will be appreciated that in this
embodiment, the heat exchange between the WGS Carboniser and the Calciner may be optimised,
in as much as no physical transfer of the sorbent is required "between" the decarboniser
and the calciner. In this embodiment, elements used for controlling the CO
2 partial pressures in the first and second segments 506, 510 have been omitted.
[0108] In one embodiment, the heating of the sorbent by the combustion process can be accommodated
by switching the input stream 501 to a stream of combustion gas and air, or a hot
flue gas from an external combustor, by valves (not shown), opening valves 508, 504,
516 and 518, closing valves 512 and 514 and switching the exhaust gases that pass
through valves 516 and 518 from a CO2 compression system to a flue stack by valves
(not shown) so that the CO2 stream is not contaminated by the flue gas. The process
can be configured to be continuous by using two or more reactor systems 502 shown
in Figure 5 and switching the combustion gas between the two reactor systems. In another
embodiment, the heating of the sorbent can be accommodated by external heat transfer
through the walls of the reactor system 502 shown in Figure 5, with the heating cycles
to each segment 506, 510 timed to provide the heat required to sustain the respective
reactions in the segments 506, 510.
[0109] Figure 6 shows a flowchart 600 illustrating a method for processing an input fuel
gas and steam to produce separate CO
2 and output fuel gas streams, according to an example embodiment. At step 602, a decarboniser
segment is used for reacting at least a solid sorbent reacts with the fuel gas and
steam to remove carbon from the input fuel gas and to produce the output fuel gas
stream in an exhaust gas from the decarboniser. At step 604, a calciner segment is
used for reacting the solid sorbent from the decarboniser segment therein to release
the CO
2 into the CO
2 gas stream, wherein CO
2 partial pressures and temperatures in the decarboniser and calciner segments respectively
are controlled such that the temperature in the decarboniser segment is higher than
the temperature in the calciner.